Vinyl-phenyl pyridine monomers and polymers prepared thereform

ABSTRACT

The present invention relates to vinyl-phenyl monomers and polymers prepared therefrom. More particularly, the present invention is to provide the vinyl-phenyl monomers expressed by formula (1) which are capable of various polymerization such as radical polymerization, cation polymerization, anion polymerization and metallocene catalyzed polymerization due to resonance effect of phenyl group and changing characteristics variously and thus, suitable in the synthesis of general-purpose polymers which can be used in photo-functional materials by forming a complex with a metal component having an optical characteristic.

BACKGROUND OF THE INVENTION

[0001] The present invention relates to vinyl-phenyl monomers andpolymers prepared therefrom. More particularly, the present invention isto provide the vinyl-phenyl monomers expressed by formula (1) which arecapable of various polymerization such as radical polymerization,cationic polymerization, anion polymerization and metallocene catalyzedpolymerization due to the resonance effect of phenyl group and changingcharacteristics variously and thus, suitable in the synthesis ofpolymers which can be used in photo-functional materials by forming apolymer complex with a metal component having an optical characteristic.

[0002] Continuous polymerization can be divided to ionic polymerizationand radical polymerization depending on an initiator. It is difficult todo a controlled polymerization due to side reaction with the radicalchain ends in radical polymerization, and reaction termination for therepulsion between the functional groups chain ends in ionicpolymerization. Reactivity of radical polymerization varies withresonance stability of vinyl group and that of ionic polymerizationvaries with the polarity.

[0003] (a) Radical Polymerization (b) Anionic Polymerization (c)Cationic Polymerization

[0004] Monomers used in continuous polymerization can be polymerized bymeans of radical, cationic or anionic polymerization depending on Q-evalue shown in the following table. Especially, either cationic oranionic polymerization can be expected with e value representing thedegree of polarity. Cationic Anionic Monomer O e PolymerizationPolymerization

0.02 −1.8

X

0.96 −1.27

O

1.00 −0.80 O O

0.42 0.62 X O

0.60 1.20 X

[0005] The polarity of a monomer is important in anionic polymerizationbecause reactivity is highly dependent on the polarity of the monomer.That is, a selection of monomers plays an essential role in thesynthesis of block copolymers. A monomer having an electron-withdrawingcharacter in vinyl group is preferable for anionic polymerization.Representative anionic monomers are styrene, α-methylstyrene, butadieneand isoprene which undergo the polymerization with a carbanion havingstrong reactivity because they have −e values. The order ofpolymerization is α-methylstyrene, isoprene and sterene.

[0006] Polymers having functional groups can be widely used forphoto-functional materials. In order to polymerize styrene, butadieneand methacrylate having a variety of functional groups through anionicpolymerization, it is required to protect the functional groups duringthe polymerization to prevent from the termination reaction betweencarbanion and the functional groups. S. Nakahama et. al have reportedthat sterene monomer having amine, hydroxy, carbonyl, carboxyl, ormercapto group can be protected with an appropriate protecting groupsuch as trimethyl silyl, t-butyldimethyl silyl, oxazoline and estergroups during the polymerization and the protected functionality is thendeprotected to regenerate the original functional group after thepolymerization [S. Nakahama, Prog. Polym. Sci., 15, 299 (1990);Makromol, Chem., 186, 1157 (1985); Polymer, 28, 303(1987);Macromolecules, 19, 2307 (1986); ibid. 26, 4995 (1993); ibid. 26, 35(1993); of Macromolecules, 20, 2968 (1987); ibid. 24, 1449 (1991); ibid.26, 6976 (-1993); Macromolecules, 19, 2307 (1986); ibid. 21, 561 (1988);ibid. 22, 2602 (1989)]. And further, the research and development ofphoto conductive and organic light emitting devices usingphenylpyridines have been actively studied and some examples have beenreported [Alistair J. Lee, Chem. Rev. 1987, 87, 711-743; M. A. Baldo, S.Lamansky, P. E. Burrows, M. E. Thompson, S. R. Forrest, Appl. Phys.Lett., 75, 4, (1.999); Raymond C. Kwong, Sergey Larnansky, and Mark E.Thompson, Adv. Mater., 2000, 12, No. 15, 1134; Catherine E. Housecroft,Coordination Chemistry Reviews, 152, (1996),141 156; K. Dedelan, P. I.Djurovich, F. O. Garces, G. Carlson, R. J. Watts, Inorg. Chem., 1991,30, 1687-1688; King, K. A, Spellane, P. J., Watts, R. J., J. Am. Chem.Soc., 1985, 107,1431].

[0007] However, the study of phenylpyridines is limited to only organicmolecule and there is no report in the synthesis of the correspondingpolymers using phenylpyridine monomers.

[0008] The present invention is to provide 2-(4-vinyl-phenyl)pyridinemonomers and polymers with controllable molecular weight and molecularstructure which can be widely useful for photo-functional materialssince said polymers of such monomers is reliable to form a complex of ametal component (iridium, ruthenium and the like).

SUMMARY OF THE INVENTION

[0009] Vinyl-phenyl monomers of formula (1) of the present invention arecapable of various polymerization such as radical polymerization, cationpolymerization, anion polymerization and metallocene catalyzedpolymerization due to the resonance effect of the phenyl group.

[0010] The molecular weight and molecular structure of polymers can becontrolled during the polymerization and the prepared polymers canfurther form a complex with various metal components such as iridium,ruthenium and the like to be useful for photo-functional materials.

[0011] Therefore, an object of the present invention is to providevinyl-phenyl pyridine monomers and the preparation method thereof whichcan be easily introduced to synthesize polymers with the controlledfunctional groups and thus, such polymers can be applied in thepreparation of thin film or fiber depending on the purpose.

[0012] Another object of the present invention is to provide thepolymers prepared by using the monomers of formula (1).

[0013] Further objection of the present invention is to provide acomplex of the polymers and iridium, ruthenium or platinum havingoptical character.

BRIEF DESCRIPTION OF THE INVENTION

[0014]FIG. 1 represents ¹H-NMR spectrum of 2-(4-vinyl-phenyl)pyridine.

[0015]FIG. 2 represents ¹³C-NMR spectrum of 2-(4-vinyl-phenyl)pyridine.

[0016]FIG. 3 represents FT-IR spectrum of 2-(4-vinyl-phenyl)pyridine.

[0017]FIG. 4 represents DSC spectrum of 2-(4-vinyl-phenyl)pyridine.

[0018]FIG. 5 represents Mass spectrum of 2-(4-vinyl-phenyl)pyridine.

[0019]FIG. 6 represents ¹H-NMR spectrum ofpoly[2-(4-vinyl-phenyl)pyridine].

[0020]FIG. 7 represents FT-IR spectrum ofpoly[2-(4-vinyl-phenyl)pyridine].

[0021]FIG. 8 represents DSC spectrum ofpoly[2-(4-vinyl-phenyl)pyridine].

[0022]FIG. 9 represents TGA spectrum ofpoly[2-(4-vinyl-phenyl)pyridine].

[0023]FIG. 10 represents GPC spectrum ofpoly[2-(4-vinyl-phenyl)pyridine].

[0024]FIG. 11 represents ¹H-NMR spectrum ofpoly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbazole].

[0025]FIG. 12 represents FT-IR spectrum ofpoly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbazole].

[0026]FIG. 13 represents GPC spectrum ofpoly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbazole].

[0027]FIG. 14 represents ¹H-NMR spectrum ofpoly({[2-(4-vinyl-phenyl)pyridine](phenylpyridine)₂iridium}-co-9-vinylcarbazole).

[0028]FIG. 15 represents FT-IR spectrum ofpoly({[2-(4-vinyl-phenyl)pyridine](phenylpyridine)₂iridium}-co-9-vinylcarbazole).

[0029]FIG. 16 represents UV and PL spectrum ofpoly({[2-(4-vinyl-phenyl)pyridine](phenylpyridine)2iridium}-co-9-vinylcarbazole).

DETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention is characterized by vinyl-phenyl pyridinemonomers expressed by the following formula (1).

[0031] The present invention is described in detail as set forthhereunder.

[0032] Examples of vinyl-phenyl pyridine monomers of the presentinvention are 2-(2-vinyl-phenyl)pyridine, 2-(3-vinyl-phenyl)pyridine,and 2-(4-vinyl-phenyl)pyridine.

[0033] The vinyl-phenyl pyridine monomers of formula (1) are prepared bythe following methods.

[0034] The first is Suzuki coupling reaction as shown in Scheme 1.

[0035] In Scheme 1, the vinyl-phenyl pyridine of formula (1) is preparedby Suzuki coupling reaction of vinyl-phenylboronic acid of formula (2)and 2bromopyridine of formula (3) in the presence of alkali metallicbase and palladium catalyst. Examples of alkali metallic base used aresodium carbonate, potassium carbonate, sodium hydroxide and potassiumhydroxide. Examples of palladium catalyst aretetrakis(triphienylphosphine)palladium (Pd(PPh₃)₄) and palladiumacetate. Examples of reaction solvent are tetrahydrofuran (THF),N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and toluene. TheSuzuki coupling reaction is performed at a temperature of from 80 to120° C.

[0036] The second is Suzuki coupling reaction and Wittig reaction asshown in Scheme 2.

[0037] In Scheme 2, formylphenyl pyridine of formula (5) is prepared bySuzuki coupling reaction of formylphenylboronic acid of formula (4) and2bromopyridine of formula (3) in the presence of alkali metallic baseand palladium catalyst and further, Wittig reaction of the preparedformylplenyl pyridine of formula (5) is performed in the presence ofmethyltriphenylphosphonium bromide (PPh₃CH₃Br) and sodium hydride toyield vinyl-phenyl pyridine of formula (1). Examples of alkali metallicbase used in Suzuki coupling reaction are sodium carbonate, potassiumcarbonate, sodium hydroxide and potassium hydroxide and examples ofpalladium catalyst are tetrakis(triphenylphosphine)palladium (Pd(PPh₃)₄)and palladium acetate. Examples of reaction solvent are tetrahydrofuran(THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), andtoluene. The Suzuki coupling reaction is performed at a temperature offrom 80 to 120° C. and Wittig reaction is from 90 to 130° C.

[0038] Besides Suzuki coupling and Wittig reactions, there are otherreactions such as Stille coupling reaction using trimethyltin chlorideor tributyltin chloride, Grignard reaction using magnesium and nickelcatalyst and coupling reaction using zinc, bipyridine,triphenylphosphine and nickel chloride to prepare vinyl-phenyl pyridinemonomers.

[0039] The present invention is also characterized by polymers preparedwith the vinyl-phenyl pyridine monomers of formula (1) which can hehomopolymers or copolymers. Particular monomers used in Ilepolymerization are 4-(9-carbazoylcarbozoyl)methyl styrene,2-(N-carbazoyl)ethyl methacrylate, and 3-(vinyl-9-ethyl)carbazole.

[0040] Conventional polymerizations of such monomers are performed.Polymerization methods are not limited and can be any one of bulkpolymerization, solution polymerization, and suspension polymerization.Polymerization system can be radical polymerization, cationicpolymerization or anionic polymerization. A polymerization initiator canbe any conventional initiator which is generally used in thepolymerization of styrene-based monomers. Particular examples ofpolymerization initiator include azobisisobutyronitrile (AIBN), benzoylperoxide, hydrogen peroxide, cumyl peroxide, tert-butyl peroxide,tert-butyl hydroperoxide, lauroyl peroxide and the like. The content of2-(4-vinyl-phenyl)pyridine can be controlled depending on the purpose inthe range of from 0.01 to 99.9%.

[0041] Number average molecular weight, weight average molecular weight,and molecular weight distribution (M_(w)/M_(n)) of the prepared polymersare analyzed by GPC and the content of the vinyl-phenyl pyridine isanalyzed by FT-NMR and FT-IR.

[0042] Examples of polymers of the present invention are the followingformulas 6-8,

[0043] wherein n+m=100 and n is an integer of 0.01 to 99.99.

[0044] The present invention is further characterized by a complex ofthe prepared polymers and a metal such as iridium, ruthenium andplatinum which is useful for photo-functional materials. Representativeexample of the complex is the following formula 9,

[0045] wherein M represents iridium, ruthenium or platinum; and n+m=100and n is an integer of 0.01 to 99.99.

[0046] Example of preparation method of the polymer complex is shown inthe following Scheme 3.

[0047] In Scheme 3, iridium(III) acetylacetonate (Iracac) and 2equivalents of 2-phenylpyridine are reacted in glycerol and then 1equivalent of the polymer having 2-(4-vinyl-phenyl)pyridine is added andheated at reflux. After the reaction is completed, the reaction mixtureis poured into aqueous hydrogen chloride solution and then extractedwith chloroform. The residue is precipitated out fromchloroform/methanol solution. The crude product is purified by columnchromatography and dried to obtain the desired polymer complex. Suchpolymer complex is very useful for photo-functional materials.

[0048] The following examples are intended to be illustrative of thepresent invention and should not be construed as limiting the scope ofthis invention defined by the appended claims.

Example 1 Preparation of 2-(4-vinyl-phenyl)pyridine

[0049] 4-Vinyl-phenylboronic acid (10 g, 0.0676 mol), 2-bromopyridine(12.64 g, 0.08 mol), tetrahydrofuran (100 ml), 2M potassium carbonateaqueous solution (26 ml), and tetrakis(triphenylphosphine) palladium(Pd(Ph₃)₄, 0.06 g, 1 mol %) were placed into 250 ml of 2-neckedround-bottomed flask under N₂. The reaction mixture was refluxed at 80°C. for 24 hr and then poured in 200 ml of water in beaker. The reactionmixture was extracted with ether (3×150 ml) and the ether layer was thendried over magnesium sulfate (10 g) by stirring for 30 min. The driedether layer was evaporated in vacuo to dryness and purified further bycolumn chromatography on silica gel with eluting hexane/ethylacetate(1/9) to yield 2-(4-vinyl-phenyl)pyridine (90%).

[0050] mp: 19.3° C.; bp: 115° C./1 mmHg; ¹H-NMR, ¹³C-NMR, FT-IR, GC andMass spectra were shown in FIGS. 1-5.

Example 2 Preparation of 2-(3-vinyl-phenyl)pyridine

[0051] The reaction was performed with 3-vinyl-phenylboronic acid (10 g,0.0676 mol), 2-bromopyridine (12.64 g, 0.08 mol), tetrahydrofuran (100ml), 2M potassium carbonate aqueous solution (26 ml), andtetrakis(triphenylphosphine) palladium (Pd(Ph₃)₄, 0.06 g, 1 mol %)according to Example 1. The yield was 80%.

Example 3 Preparation of 2-(2-vinyl-phenyl)pyridine

[0052] The reaction was performed with 2-vinyl-phenylboronic acid (10 g,0.0676 mol), 2-bromopyridine (12.64 g, 0.08 mol), tetrahydrofuran (100ml), 2M potassium carbonate aqueous solution (26 ml), andtetrakis(triphenylphosphine) palladium (Pd(Ph₃)₄, 0.06 g, 1 mol %)according to Example 1. The yield was 75%.

Example 4 Preparation of 2-(4-vinyl-phenyl)pyridine

[0053] 4-Formylphenylboronic acid (10.14 g, 0.0676 mol), 2-bromopyridine(12.64 g, 0.08 mol), tetrahydrofuran (100 ml), 2M potassium carbonateaqueous solution (26 ml), and palladium acetate (Pd(OAc)₂, 0.04 g, 1 mol%) were placed into 250 ml of 2-necked round-bottomed flask under N₂.The reaction mixture was refluxed at 90° C. for 24 hr and then poured in200 nil of water in beaker. The reaction mixture was extracted withether (3×150 ml) and the ether layer was then dried over magnesiumsulfate (10 g) by stirring for 30 min. The dried ether layer wasevaporated in vacuo to dryness and purified further by columnchromatography on silica gel with eluting hexane/ethylacetate (1/5) toyield 2-(4-vinyl-phenyl)pyridine (80%).

Example 5 Preparation of 2-(4-vinyl-phenyl)pyridine

[0054] Methyltriphenylphophonium bromide (25 g, 0.07 mol), sodiumhydride (NaH, 3.36 g, 0.14 mol), and toluene (100 ml) were placed into250 ml of 2-necked round-bottomed flask under N₂. The reaction mixturewas refluxed at 110° C. for 3 hr while changing the reaction solution toorange color. After cooling the reaction mixture,2-(4-formyl-phenyl)pyridine (10 g, 0.0545 mol) was added and furtherrefluxed at 110° C. for 12 hr. The reaction mixture was poured in 300 mlof water in beaker and extracted then with ether (3×150 ml). The etherlayer was then dried over magnesium sulfate (10 g) by stirring for 30min. The dried ether layer was evaporated in vacuo to dryness andpurified further by column chromatography on silica gel with elutinghexane/ethylacetate (1/10) to yield 2-(4-vinyl-phenyl)pyridine (85%).

Example 6 Preparation of poly[2-(4-vinyl-phenyl)pyridine]homopolymner

[0055] 2-(4-Vinyl-phenyl)pyridine (0.5 g, 2.761 mmol) andazobisisobutyronitrile (AIBN, 0.0045 g, 2.761 mmol) were placed into 10ml of round-bottomed flask under N₂. The reaction mixture was bulkpolymerized at 75° C. for 30 min, dissolved in chloroform (15 ml), andfiltered through 0.2 μm Teflon filter. The filtrate was dropped into 200ml of methanol to precipitate out while stirring. The precipitate wasfiltered through glass filter to collect the polymer product which wasfurther dried in vacuum oven at 60° C. for 24 hr. The yield was 95%. Thepolymer was analyzed to have 54,000 g/mole of number average molecularweight, 230,000 g/mole of weight average molecular weight and 4.32 ofmolecular weight distribution (M_(w)/M_(n)). ¹H-NMR, 13C-NMR, FT-IR, GCand Mass spectra were shown in FIGS. 6-10.

Example 7 Preparation ofpoly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbozole]copolymer

[0056] 2-(4-Vinyl-phenyl)pyridine (0.5 g, 2.76 nmmol), 9-vinylcarbazole(2.22 g, 110.9 mmol) and azobisisobutyronitrile (0.015 g, 1 mol %) werebulk-polymerized at 75° C. for 30 min, dissolved in chloroform (20 ml),and filtered through 0.2 μm Teflon filter. The filtrate was dropped into250 ml of methanol to precipitate out while stirring. The precipitatewas filtered through glass filter to collect the polymer product whichwas further dried on vacuum oven at 60° C. for 24 hr. The yield was 87%.The prepared poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbozole]copolymer having 20% content of 2-(4-vinyl-phenyl)pyridine was analyzedto have 43,000 g/mole of number average molecular weight, 71,000 g/moleof weight average molecular weight and 1.65 of molecular weightdistribution (M_(w)/M_(n)). ¹H-NMR, ¹³C-NMR, FT-IR, GC and Mass spectrawere shown in FIGS. 11-16.

Example 8 Preparation ofpoly[2-(4-vinyl-phenyl)pyridine-co-4-(9-carbozoyl)methylstyrene]copolymer

[0057] By the same procedure as described in Example 7,poly[2-(4-vinyl-phenyl)pyridine-co-4-(9-carbozoyl)methyl styrene]copolymer having 20% content of 2-(4-vinyl-phenyl)pyridine was preparedexcept using 4-(9-carbazolyl)methyl styrene instead of 9-vinylcarbazolein 80%.

Example 9 Preparation ofpoly[2-(4-vinyl-phenyl)pyridine-co-2-(vinyl-9-ethyl)carbozole]copolymer

[0058] By the same procedure as described in Example 7,poly[2-(4-vinyl-phenyl)pyridine-co-3-(vinyl-9-ethyl)carbozole] copolymerhaving 20% content of 2-(4-vinyl-phenyl)pyridine was prepared exceptusing 2-(N-carbazoyl)ethyl methacrylate instead of 9-vinylcarbazole in87%.

Example 10 Preparation ofpoly[2-(4-vinyl-phenyl)pyridine-co-3-(vinyl-9-ethyl)carbozole]copolymer

[0059] By the same procedure as described in Example 7,poly[2-(4-vinyl-phenyl)pyridine-co-2-(vinyl-9-ethyl)carbozole]copolymerhaving 20% content of 2-(4-vinyl-phenyl)pyridine was prepared exceptusing 3-(vinyl-9-ethyl)carbazole instead of 9-vinylcarbazole in 90%.

Example 11 Preparation ofpoly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbozole]copolymer

[0060] By the same procedure as described in Example 6,poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbozole]copolymer having 12%content of 2-(4-vinyl-phenyl)pyridine was prepared using2-(4-vinyl-phenyl)pyridine (0.4 se, 2.2 mmol), 9-carbazole (2 g, 10.3mmol) and azobisisobutyronitrile (0.021 g), −1 mol %). The copolymer has22,000 g/mole of number average molecular weight, 57,000 g/mole ofweight average molecular weight and 2.56 of molecular weightdistribution (M_(w)/M_(n)).

Example 12 Preparation ofpoly{[(2-(4-vinyl-phenyl)pyridine)(phenylpyridine)₂iridium]-co-9-vinylcarbazole}

[0061] Iridium(III) acetylacetonate (0.5 g, 1.02 mmol), 2-phenylpyridine(0.32 g, 2.04 mmol), and glycerol (50 ml) were placed into 250 ml of2-necked round-bottomed next flak. The reaction mixture was refluxed at170° C. for 3 hr. Poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbozole]copolymer (0.32 g, 2.04 mmol) prepared in Example 11 and chloroform (50ml) were added and further refluxed for 24 hr. The reaction mixture waspoured into 200 ml of 1N hydrogen chloride aqueous solution andextracted with chloroform. The chloroform layer was evaporated todryness. The residue was dissolved in chloroform (10 ml) andprecipitated out from 200 ml of 99.9% methanol. The precipitate wasfiltered through glass filter to collect the polymer complex which wasfurther dried on vacuum oven at 60° C. for 24 hr. The field was 95%. Thepolymer was analyzed to have 43,000 g/mole of number average molecularweight, 71,000 g/mole of weight average molecular weight and 1.65 ofmolecular weight distribution (M_(w)/M_(n)). ¹H-NMR, FT-IR, UV and PLspectra were shown in FIGS. 14-16.

[0062] Vinyl-phenyl monomers of the present invention are capable ofvarious polymerization such as radical polymerization, cationpolymerization, anion polymerization and metallocene catalyzedpolymerization due to resonance effect of phenyl group unlike othermonomers. Such vinyl-phenyl monomers can be polymerized to homopolymersor copolymers. Molecular weight and molecular structure of polymers canbe controlled during the polymerization and the polymers with thecontrolled weight and structure can further incorporate with a metalsuch as iridium, ruthenium and platinum to form a polymer-metal complexwhich is useful in a variety of fields using photo-functional materials.

What is claimed is:
 1. Vinyl-phenyl monomers expressed by the followingformula (1).


2. A preparing method of vinyl-phenyl monomers of formula (1) by Suzukicoupling reaction of vinyl-phenylboronic acid of formula (2) and2-bromopyridine of formula (3) in the presence of alkali metallic baseand tetrakis(triphenylplhosphine) palladium.


3. A preparing method of vinyl-phenyl monomers of formula (1) by Suzukicoupling reaction of formylphenylboronic acid of formula (4) and2-bromopyridine of formula (3) in the presence of alkali metallic baseand palladium catalyst to generate formylphenyl pyridine of formula (5)and further Wittig reaction of the prepared formylphenyl pyridine offormula (5) in the presence methyltriphenylphosphonium bromide(PPh₃CH₃Br) and sodium hydride.


4. A homopolymer having the formula (6) as a repeating unit.


5. A copolymer expressed by the following formula (7),

wherein n+m=100 and n is an integer of 0.01 to 99.99.
 6. A copolymerexpressed by the following formula (8),

wherein n+m=100 and n is an integer of 0.01 to 99.99.
 7. A polymercomplex expressed by the following formula (9),

wherein M represents iridium, ruthenium or platinum; and n+m=100 and nis an integer of 0.01 to 99.99.